These Ozcan 19 Mars 2010

Graduate School of Sciences Electroanalytical Research Laboratory at Chemistry Department
Institut Francilien des Sciences Appliques Laboratoire Gomatriaux et Environnement
DOCTORAL THESIS To obtain the degree of Doctor of the "University of Paris-Est"- France and "Anadolu University"- Turkey Speciality: Environmental Science and Techniques
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Ali OZCAN
March 19th, 2010
DEGRADATION OF HAZARDOUS ORGANIC COMPOUNDS BY USING ELECTRO-FENTON TECHNOLOGY
DEGRADATION DES POLLUANTS ORGANIQUES PAR LA TECHNOLOGIE ELECTRO-FENTON
Supervisors:
Jury: Reviewers:
Prof. Mehmet A. OTURAN (Universit Paris-Est) Prof. Ycel SAHIN (Anadolu University)
Prof. Figen KADIRGAN Prof. Otavio GIL
Istanbul Technical University Universit de Caen Basse Normandie Hacettepe University Universit Paris-Est
Examinators: Prof Kadir PEKMEZ

Dr. Nihal OTURAN
Acknowledgement
This thesis has been carried out at the Electroanalytical Research Laboratory of Chemistry Department and Laboratoire Gomatriaux et Environnement in the frame of convention for the joint supervision of thesis between Anadolu University and University of Paris-Est. First of all, I wish to express my heartfelt thanks to the laboratory directors, Prof. Dr. Mehmet A. OTURAN and Prof. Dr. Ycel AHN for giving me the chance to conduct the experiments. I would like to acknowledge my sincere gratitude to my supervisors, Prof. Dr. Mehmet A. OTURAN and Prof. Dr Ycel AHN for their endless support, innovative guidance and continuous encouragement throughout this work.
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I want to express my gratitude to reviewers of this thesis, Prof. Dr. Figen KADIRGAN (Istanbul Technical university) and Prof. Dr. Otavio GIL (Universit de Caen Basse Normandie) for accepting to read and evaluate my work and for providing valuable suggestions and comments. I wish to thank my dissertation committee, Prof. Dr. Mehmet A. OTURAN, Prof. Dr. Ycel AHN, Prof. Dr. Figen KADIRGAN, Prof. Dr. Otavio GIL, Prof. Dr. Kadir PEKMEZ (Hacettepe university-Ankara) and Dr. Nihal OTURAN for their valuable comments and suggestions on this work. I gratefully acknowledge financial support of Anadolu University Research Found (Project No: 061022). A very special thanks to Prof. Dr. Mehmet A. OTURAN, Dr. Nihal OTURAN and their family for their hosptality during my studies in France. I would like to thank to Prof. Dr A. Sava KOPARAL (Anadolu University-Eskisehir) for his support, suggestions and comments. I thank to Anadolu University Plant, Drug and Scientific Researches Center and Erol ENER for performing the LC-MS analysis. I also would like to thank to my colleaques of the Chemistry Department, especially to Levent ZCAN for their assistance, their support and friendship. I express my gratitude to The Scientific and Technical Research Council of Turkey (TUBITAK) Scientific Human Resources Development (BAYG) for the fellowship.
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Finally, I would like to dedicate the thesis to my wife Aya Atlr ZCAN and my son Hasan Berk ZCAN and all my family for their guidance, support, love and enthusiasm. Without these things this thesis could not have been possible.
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ABSTRACT
In this thesis, a detailed investigation has been carried out on the use of electro-Fenton technique for the oxidation of the some persistent organic pollutants for the sake of water remediation. This technique produces OH radicals electrocatalytically and uses them to oxidize the organic pollutants. The overall study can be divided into three parts. In the first part, the removal of selected synthetic dyes and pesticides from water was investigated by using carbon felt (CF) cathode. The oxidation kinetics of the synthetic dyes (Acid Orange 7 and Basic Blue 3) and pesticides (picloram, propham, azinphos-methyl and clopyralid) were determined. Mineralization kinetics of the related organic pollutants in aqueous medium was followed by total organic carbon and chemical oxygen demand analysis. The overall mineralization was
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obtained in all cases. Identification and quantification of the oxidation by-products of the given synthetic dyes and pesticides were performed by high performance liquid chromatography, gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry and ion chromatography. These systematic analysis showed that the initial organic pollutants were converted into three intermediate forms; organic intermediates, shortchain aliphatic carboxylic acids and inorganic ions. Based on the intermediates identified, a plausible mineralization pathway was proposed for each dye and pesticide. In the second part of the study, the H2O2 production ability of carbon sponge (CS) as a novel cathode material for the electro-Fenton technique was investigated for the first time in the literature. The obtained results indicated that CS has a H2O2 production ability three times higher than the classical cathode CF. In the third and last part, the efficiency of boron doped diamond (BDD) as an anode in the electro-Fenton technique was investigated. Firstly, the oxidation and mineralization ability of BDD was tested for herbicide propham in anodic oxidation conditions. Then, the combination of CS and BDD electrode in the electro-Fenton technique was examined. The obtained results indicated that this combination allowed the most efficient results throughout the thesis. Moreover, the use of BDD anode in the electro-Fenton technique had considerable effect on the oxidation and mineralization of organics and especially carboxylic acids such as oxalic and oxamic acids which were highly resistant to mineralization in the case of Pt anode.
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RESUME
Une tude dtaille a t effectue sur l'utilisation de la technique lectro-Fenton pour l'oxydation de quelques polluants organiques persistants (POP) dans le but du traitement des eaux uses. Cette technique gnre, in situ et de manire lectrocatalytique, les radicaux hydroxyles (OH) afin de les utiliser pour oxyder la polluants organiques. Le travail de thse est constitu en trois parts. Dans la premire partie, l'limination de l'eau des colorants synthtiques et pesticides choisis comme polluants modles a t effectue en utilisant une cathode en feutre de carbone. Les cintiques d'oxydation des colorants synthtiques (Acide Orange 7 et Bleu Basique 3) et des pesticides (picloram, prophame, azinphos-mthyl et clopyralid) ont t dtermines. La cintique de minralisation des solutions aqueuses des polluants organiques en question a t suivie par des analyses de
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carbone organique totale (COT) et demande chimique en oxygne (DCO). Une minralisation quasi-totale a t obtenue dans tous les cas. L'identification et la quantification des sousproduits d'oxydation des colorants synthtiques et pesticides ont t effectues par les techniques d'analyse suivantes: Chromatographie liquide haute performance (CLHP), chromatographie en phasegazeuse-spectromtrie de masse (GC/MS), chromatographie liquide haute performances-pctromtrie de masse (HPLC/MS) et chromatographie ionique. Ces analyses systmatique ont mis en vidence que les polluants organiques initiaux ont sont convertis en trois formes d'intermdiaires ractionnels; intermdiaires organiques, acides carboxyliques courte chane et ions inorganiques. Bas sur l'identification ces des intermdiaires ractionnels, une schma de minralisation plausible a t propos pour chaque colorant et pesticide tudi. Dans la deuxime partie de l'tude, la capacit de production de peroxyde d'hydrogne (H2O2) de la cathode en ponge de carbone comme matriau original de cathode pour la technique lectro-Fenton a t tudie pour la premire fois. Les rsultats obtenus ont indiqu que le l'ponge de carbone possde une capacit de la production d'H2O2 trois fois plus leve par rapport la cathode classique (feutre de carbone). La troisime et dernire partie de cette thse a t consacre l'tude de l'efficacit et l'utilisation en lectro-Fenton d'une anode de nouvelle gnration, le diamant dop au bore (BDD pour "Boron Doped Diamond"). Tout d'abord, l'efficacit d'oxydation et la capacit de minralisation de l'anode BDD ont t examines sur l'herbicide propham dans les conditions d'oxydation anodique. Ensuite, la combinaison de cathode en feutre de carbone et l'anode BDD dans la technique lectro-Fenton a t examine. Les rsultats obtenus ont montr que
cette combinaison conduit aux rsultats significativement meilleurs que le systme classique feutre de carbone - Pt. L'utilisation de l'anode BDD dans l'lectro-Fenton amliore considrablement la cintique d'oxydation et l'efficacit de minralisation des polluants
organiques et en particulier des acides carboxyliques tels que les acides oxalique et oxamique qui rsistent la minralisation dans le cas de l'anode Pt.
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SUMMARY
1. INTRODUCTION 1
1.1. Principles of electrochemical advanced oxidation processes. 1 1.2. Criteria for selection of organic pollutants. 3 1.3. Objectives of study.5
2. EXPERIMENTAL SECTION
2.1. Electrochemical system.. 6 2.2. Analytical Measurements...6
3. RESULTS AND DISCUSSION
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3.1. Removal of selected hazardous organic pollutants

by electro-Fenton technology using carbon felt (CF) cathode...8 3.1.1. Synthetic dyes..... 8 3.1.1.1. Acid orange 7.. 9 Paper 1..11 3.1.1.2. Basic Blue 3. 20 Paper 2. 22 3.1.2. Pesticides32 3.1.2.1. Picloram... 33 Paper 3. 36 3.1.2.2. Propham... 47 Paper 4. 50 3.1.2.3. Clopyralid 59 Paper 5. 62 3.1.2.4. Azinphos-Methyl. 72 Paper 6. 74 3.2. Investigation of the H2O2 production ability of carbon sponge (CS) as a novel cathode material for electro-Fenton process.......... 79 Paper 7. 82 3.3. Investigation of the efficiency of boron doped diamond (BDD) anode in the electro-Fenton process... 91
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Paper 8. 95 Paper 9. 106 REFERENCES CURRICULUM VITEA 114 120
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1.
INTRODUCTION
1.1. Principles of Electrochemical Advanced Oxidation Processes

Water is of fundamental importance for life on the Earth. The whole mechanism of metabolism, the synthesis and structure of colloidal cellular constituents, the solution and transport of nutrients inside the cells and interactions with the environment are closely related to the specific characteristics of water. On the other hand, the part of the freshwater (grounwater, lakes and rivers, polar ice and glaciers in height) that can be used by the human beings is only 2.66% of the global water resource. Furthermore, these freswater resources, in particular surface water is
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exposed to the pollution coming from various human activity. Therefore, in order to protect natural water resources it is necessary to treat efficiently wastewater effluents before their injection in the natural water system. Common physico-chemical wastewater treatment methods such as activated carbon adsorption and membrane filtration transform the pollutants from one phase to another, so they separate but not eliminate the water pollutants. Ozone and hypochlorite oxidations are efficient methods for water disinfection but remain inefficient in case of effluents of hard COD (effluents from industrial or agricultural activities). On the other hand, they are not desirable because of the high cost of equipment, operating costs and the secondary pollution arising from the residual chlorine (Malik and Saha, 2003). Recent progress in the treatment of persistent organic pollutants (POPs) in water and/or wastewater has led to the development of advanced oxidation processes (AOPs). These processes involve chemical, photochemical or electrochemical techniques to bring about chemical degradation of organic pollutants. The most commonly used oxidation processes use H2O2, O3 or O2 as the bulk oxidant to form principal active specie in such systems, i.e., the hydroxyl radical, OH, a highly oxidizing agent of organic contaminants (Lin and Lo, 1997; Huston and Pignatello, 1999; Oturan, 2000; Dutta et al., 2001; Malik and Saha, 2003; Swaminathan et al., 2003; Pignatello et al., 2006. Brillas et al., 2009). These radicals react with organic pollutants and thus lead to their degradation by hydrogen abstraction reaction
(dehydrogenation), by redox reaction or by electrophilic addition to systems (hydroxylation) (Oturan, 2000). The most commonly used AOPs for the removal of persistent organic pollutants from water are based on the Fentons reaction. However, this reaction has some limitations in application such as the use of large quantities of chemical reagents, large production rates of ferric hydroxide sludge and slow catalysis of the ferrous ions generation (Boye et al., 2002; Brillas et al., 2004). Electrochemical AOPs overcome these drawbacks and offer many advantages such as low operational cost and high mineralization degree of pollutants compared to other known chemical and photochemical ones. In this sense, anodic oxidation and electro-Fenton processes are very commonly used electrochemical AOPs.
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In anodic oxidation, pollutants are mineralized by direct electron transfer reactions or action of radical species (i.e. hydroxyl radicals) formed on the electrode surface. In this manner, a wide variety of electrode materials have been investigated recently, but the boron doped diamond (BDD) has attracted great attention because of its high O2 evolution overvoltage, high stability and efficiency (Chen and Chen, 2006; Guinea et al., 2008). This electrode allows to produce large quantities of hydroxyl radicals from water or hydroxide oxidation decomposition on the electrode surface (Eqs. 1.1 and 1.2) (Comminellis, 1994; Marselli et al., 2003; Michaud et al., 2003; Canizares et al., 2004; Panizza and Cerisola, 2005). The formation of H2O2 is also possible depending on the cathode materials used during the anodic oxidation process. The oxidation of formed H2O2 to HO2 (Eq. 1.3) or to O2 (Eq. 1.4) takes place at anode surface (Boye et al., 2002). The formed reactive species may react with the organics but their oxidation ability are poor compared to adsorbed OH radicals. H2O OHads +H+ +e OH OHads +e H2O2 HO2 + H+ + eHO2 O2 + H+ + e(pH10) (1.1) (1.2) (1.3) (1.4)
In the electro-Fenton process, pollutants are destroyed by the action of Fentons reagent in the bulk together with anodic oxidation at the anode surface in the case of the use of a high O2 evolution overvoltage anode such as BDD. Fentons reagent is formed in the electrolysis medium by the simultaneous electrochemical reduction of O2 to H2O2 (Eq. 1.5) and Fe (III) to Fe (II) ions (Eq. 1.6) on the cathode surface.
(Gzmen et al., 2003; Guivarch et al., 2003). The reaction between these two species in the homogeneous medium allows the formation of OH radicals (Eq. 1.7) (Oturan, 2000; Oturan et al., 2001; Brillas et al., 2005). The Eqs. 1.3 and 1.4 can also take place during the electro-Fenton process. Moreover, the oxidation of regenerated Fe2+ to Fe3+ may occur at the same time (Eq. 1.8) on the anode surface. On the other hand, the existence of these reactions (Eqs. 1.3, 1.4 and 1.8) are negligible compared to reaction (1.7) which occurs in the bulk because of the limited surface area of anode. Finally, iron species (Fe3+/Fe2+) can react with the formed reactive species from anodic and cathodic reactions (Eq. 1.9-1.11) (Sirs et al., 2007). The overall effect of these reactions influences the mineralization process of organics in the electro-Fenton treatment. O2 + 2H+ + 2e- H2O2 Fe(OH)2+ + e- Fe2+ + OHFe2+ + H2O2 + H+ Fe3+ + H2O + OH Fe2+ Fe3+ + eFe3+ + H2O2 Fe2+ + H+ + HO2 Fe3+ + HO2 Fe2+ + H+ + O2 Fe2+ + HO2 Fe3+ + HO2(1.9) (1.10) (1.11)
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(1.5) (1.6) (1.7) (1.8)
The hydroxyl radicals (OH) formed by the electrochemical (Eq. 1.1) or bulk (Eq. 1.7) are very powerful oxidizing agents. They react unselectively with organics giving dehydrogenated and/or hydroxylated reaction intermediates before their total conversion into CO2, water and inorganic ions, when OH are produced in continue. Because OH production does not involve the use of harmful chemical reagents which can be hazardous for the environment, electrochemical processes can be seen as environmentally friendly techniques. In conclusion, these processes seem to be very promising for the purification of water polluted by persistent and/or toxic organic pollutants.
1.2. Criteria for selection of organic pollutants

In this study, organic pollutants were chosen from synthetic dyes and pesticides which are the most prominent pollutants of water.
Synthetic dyes are extensively used in textile, leather, paper, pharmaceutical and food industries. They thus constitute the major components of wastewaters released from these industries. The dyes are generally designed to resist biodegradation, so they cause severe ecological and environmental problems (Allen et al., 1995). This environmental problem is highlighted by the estimation of a charge up to 50 000 tons of dye wastes discharged annually from dyeing installations worldwide (Brown, 1987). In addition, some dyes or their metabolites are either toxic or mutagenic and carcinogenic (Heiss et al., 1992; Chen et al., 2003). Thus, the treatment of the effluents containing such compounds is important for the protection of natural waters and environment. Synthetic dyes divided into two categories as acidic and basic dyes according to
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their acidic characters. We have chosen two synthetic dyes, Acid Orange 7 and Basic Blue 3, which represent these two subgroups. Natural or synthetic pesticides are used to kill various kinds of animal and plant pests. Pesticides cover a wide range of products including weedkillers, insecticides, fungicides, wood preservatives and rodenticides. Of the pesticides that are used far less than 1% actually reaches a target organism; the rest ends up contaminating the air, soil, water, plants and animals. Pesticides have been used extensively to increase the agricultural productivity as well as their household usage. Food and Agriculture Organization reported that more than 1.2 million metric tons of pesticides were sold to the agricultural sectors during the middle of the last decade (Shulze et al., 2002). These substances are in fact very effective against the harmful microorganisms, weed and insects in order to increase agricultural yields; however, because of their hazardous nature, the waste and rinsate from spray and storage equipment have been considered as one of the major threats to the environment. Thus, treatment of effluents containing pesticides is of environmental importance. In this study, we investigated the ability of the electroFenton process to eliminate three herbicides which belong to different chemical family: Picloram (systemic herbicide), propham (carbamate herbicide) and chlopyralid (systemic herbicide) and a organophosphorus non systemic insecticide: Azinphos-methyl. According to our knowlodge, the electro-Fenton removal of the selected organic pollutants were not reported before.
1.3. Objectives of Study

This study is aiming to achieve the following objectives: a) To investigate various operational parameters affecting oxidation and mineralization kinetics of the selected synthetic dyes and pesticides in the electro-Fenton technique using carbon felt cathode. b) To determine and quantify the oxidation intermediates such as aromatic indermediates, short-chain aliphatic carboxylic acids and inorganic ions as end-products formed during the electro-Fenton treatment. c) To study the mineralization reaction pathways of the related pollutants. d) To investigate the effectivenes of a novel cathode material, carbon sponge,
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in the electrogeneration of hydrogen peroxide in acidic solutions. e) To investigate the effectivenes of boron doped diamond (BDD) electrode as anode in the electro-Fenton process.
2. EXPERIMENTAL SECTION
2.1. Electrochemical System

Experiments were performed at room temperature in an undivided cylindrical glass cell equipped with two electrodes. Carbon felt, carbon sponce and Pt gauze were used as cathode. The anode was Pt gauze and boron doped diamond (BDD). Prior to the electrolysis, compressed air was bubbled through the aqueous solution, which was agitated continuously by a magnetic stirrer. In the case of electro-Fenton experiments, a catalytic quantity of iron(III) sulphate pentahydrate was introduced into the electrolysis solution and the pH of the solution was setted at 3 by addition of aqueous
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H2SO4 (1 M). The current and the amount of charge passed through the solution was measured and displayed continuously throughout electrolyses by a DC power supply. The ionic strength was maintained constant by the addition of 0.05 M Na2SO4.
2.2. Analytical Measurements

The evaluation of the concentrations of the selected organic pollutants were monitored by high performance liquid chromatography (HPLC) using an Agilent 1100 system equipped with a diode array detector and an autosampler. A reversed phase Inertsil ODS-3 (5 m ID, 4.6 mm x 250 mm) column was used in the analyses. The column was thermostated at 40 C. 20 L samples were injected. A suitable eluent mixture was used during the analysis. Carboxylic acids were identified and quantified by a Supelcogel H column ( = 7.8300 mm) which was thermostated at 40 C with a mobile phase of 4 mM H2SO4. The detection was performed at 210 nm. The formed aromatic reaction intermediates during the electrolysis of the selected hazardous organic compound were determined by HPLC, gas
chromatography coupled with mass spectroscopy (GC-MS) or liquid chromatography coupled with mass spectroscopy (LC-MS). The inorganic end-products formed during the mineralization of selected hazardous organic compound were measured by ion chromatography. A cationic
exchanger column was used to determine cationic species and an anionic exchanger column was used to determine anionic species. The total organic carbon (TOC) of the initial and treated samples was determined by a Shimadzu TOC-V analyzer. A platinium catalyst was used in the combustion reaction. The carrier gas was oxygen with a flow rate of 150 ml min1. A non-dispersive infra-red detector, NDIR, was used in the TOC system. Calibration of the analyzer was attained with potassium hydrogen phthalate (99.5%, Merck) and sodium hydrogen carbonate (99.7%, Riedel-de Han) standards for total carbon (TC) and inorganic carbon (IC), respectively. The difference between TC and IC values gives TOC value of the sample. The chemical oxygen demand (COD) analysis and hydrogen peroxide
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determination were performed according to certified analytical methods. The mineralization current efficiency (MCE) values were determined by using the following expression (Eq. 2.1) (Brillas et al., 2004; Sires et al., 2006; Diagne et al., 2007): MCE = (TOC) exp (TOC) theor 100 (2.1)
where (TOC)exp is the experimental TOC at a given time and (TOC)theor is the theoretical TOC value considering the applied electrical charge (=current x time) consumed for the complete mineralization of organic pollutant under study according to its electrochemical oxidation reaction.
3. RESULTS AND DISCUSSION

The obtained results throughout this thesis work are divided into three main sections; (i) Removal of selected hazardous organic pollutants by electro-Fenton technology using carbon felt (CF) cathode, (ii) H2O2 production ability of carbon sponge (CS) as a novel cathode material for electro-Fenton process, and (iii) Use and efficiency study of boron doped diamond (BDD) anode in the electro-Fenton process.
3.1. Removal of selected hazardous organic pollutants by electroFenton technology using carbon felt (CF) cathode
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3.1.1. Synthetic dyes

Synthetic dyes are extensively used in textile, leather, paper, pharmaceutical and food industries. They thus constitute the major components of wastewaters released from these industries. The dyes are generally designed to resist biodegradation, so they cause severe ecological and environmental problems (Allen et al., 1995). This environmental problem is highlighted by the estimation of a charge up to 50 000 tons of dye wastes discharged annually from dyeing installations worldwide (Brown, 1987). In addition, some dyes or their metabolites are either toxic or mutagenic and carcinogenic (Heiss et al., 1992; Chen et al., 2003). Thus, the treatment of the effluents containing such compounds is important for the protection of natural waters and environment. Common physico-chemical treatment methods for the decolourization of dye wastewaters such as activated carbon adsorption and extraction are able to separate these pollutants to form a concentrated waste to be treated subsequently, and so they are inefficient to eliminate the pollutants. Ozone and hypochlorite oxidations are efficient decolorizing methods, but they are not desirable because of the high cost of equipment, operating costs and the secondary pollution arising from the residual chlorine (Malik and Saha, 2003) or because of remained oxidation reaction intermediates. Other conventional processes based on biological treatment (aerobic anaerobic) are relatively ineffective in effluent decolourisation, because high
molecular weight compounds are not easily degraded by bacteria, and thus coloured compounds pass through the treatment system largely undegraded (Banat et al., 1996).
3.1.1.1. Acid orange 7
The azo dye Acid Orange 7 (AO7), also called Orange II (Fig. 3.1) is a widely used synthetic dye. It does not decompose biologically, and resists to photochemical degradation and chemical oxidation. It is generally used as a model substrat for the azo dyes. Therefore, its removal has been studied by several research groups; Bandara et al. (1996) used photo-Fenton reactions in the presence of natural sunlight, Kiwi et al. (2001) reported a catalytic photo-assisted system, Fe3+/nafion/glass fibers, Daneshvar et al. (2003) employed electrocoagulation, Ray et al. (2004) performed photocatalytic oxidation in the presence of TiO2, Ramirez et al. (2005) investigated optimum conditions for Fenton's oxidation and Inoue et al. (2006) used ultrasound waves. In addition, Daneshvar et al. (2008) were studied the electrochemical degradation of AO7 in potentiostatic conditions and obtained a mineralization ratio of 75%.
OH
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SO3Na
Figure 3.1. The molecular structure of Acid Orange 7
In this part of the study, we report a detailed discussion on the oxidative degradation of AO7 in acidic aqueous solution by the electro-Fenton process. The experiments were carried out under constant current electrolysis conditions in undivided electrochemical cell by using a carbon-felt cathode and a Pt anode. The kinetics of AO7 degradation by OH during electro-Fenton process has been examined. The absolute rate constant of the reaction between AO7 and OH was determined as (1.20 0.17) x 1010 M-1 s-1 by the competition kinetic method using benzoic acid as a reference competitor (Gzmen et et al., 2003). The effect of the applied current and catalyst concentration on the degradation of AO7 was studied.
The optimal current value and Fe2+ concentration for the degradation of AO7 were found as 300 mA and 0.1 mM, respectively. AO7 degradation rate was found to decrease by increase in Fe3+ concentration beyond 0.1 mM. Mineralization of AO7 aqueous solutions was followed by total organic carbon (TOC) measurements and the mineralization degree was found to be 92% after 8 h of treatment. The reaction between organics and hydroxyl radicals has led to the formation of aromatic intermediates, short-chain aliphatic carboylic acids and inorganic ions. Several aromatic intermediates such as 1,2-naphthaquinone, 1,2-naphthalenediol, 4aminobenzenesulfonic acid, 4-aminophenol, 4-hydroxybenzenesulfonic acid, 2formyl-benzoic acid, 2-hydroxy-1,4-naphthalenedione, 2,3-dihydroxy-1,4-
naphthalenedione, salicylic acid, 1,4-benzoquinone, hydroquinone and 1,2,4-
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benzentriol were identified by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS) analysis. Maleic, acetic, malonic, glyoxylic, formic and oxalic acids were identified as short-chain aliphatic carboxylic acids by ion exclusion chromatography. The sulphate, nitrate and ammonium was determined as final by-products by ion exchange chromatography. Based on TOC evolution and identification of aromatic intermediates, short-chain carboxylic acids and inorganic ions released during treatment, a plausible mineralization pathway was proposed.
The thorough results of this section are included in the following paper (Paper 1).
Ali zcan, Mehmet A. Oturan, Nihal Oturan, Ycel ahin, (2009). Removal of Acid Orange 7 from water by electrochemically generated Fentons reagent. Journal of Hazardous Materials, 163(2-3), 1213-1220.
The following presentations in a congress are related to this work:

Ali zcan, Ycel ahin, Nihal Oturan, Mehmet A. Oturan, Removal of Acid Orange 7 from water by electrochemically generated Fentons reagent, Journees dElectrochimie 2007, Lyon, France, 2-6 July 2007 (Poster presentation).
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Paper 1
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Ali zcan, Mehmet A. Oturan, Nihal Oturan, Ycel ahin (2009). Removal of Acid Orange 7 from water by electrochemically generated Fentons reagent. Journal of Hazardous Materials, 163(2-3), 1213-1220.
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3.1.1.2.
Basic Blue 3
Basic Blue 3 (BB3) is a cationic dye (Fig. 3.2). Cationic dyes, commonly known as basic dyes, are widely used in acrylic, nylon, silk, and wool dyeing. Due to their complex chemical structure, they are recalcitrant to treatment by chemical, physical and biological methods. Furthermore, any degradation by physical, chemical or biological treatments may produce toxic and carcinogenic products (McKay et al., 1985; Gregory et al., 1991).
N
ClN O N
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Figure 3.2. Chemical structure of BB3 ((7-Diethylamino-phenoxazin-3-ylidene)-diethylammonium chloride).
The removal of BB3 from water was already investigated by different process. Akbari et al. (2002) used a polyamide-based nanofiltration membrane for the removal of BB3 from textile dye effluent. Moreover, Daneshvar et al. (2006) used electrocoagulation for decoloration of BB3 containing solutions. Adsorption process for the removal of BB3 from water was also performed by using peat (Allen et al., 2004) and rice straw (Abdel-Aal et al., 2006). In this part of the study, we focused our effort on the identification of the oxidation reaction intermediates and the elucidation of the degradation pathway during electro-Fenton treatment of synthetic BB3 aqueous solutions. The decay of BB3 and the evolution of its oxidation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The absolute rate constant of the BB3 hydroxylation reaction has been determined as (2.61 0.06) x 109 M-1 s-1 by using the competition kinetic method. The effect of the applied current on the BB3 removal rate was examined. The optimal current value for the mineralization of BB3 aqueous solution was found as 300 mA. It was also observed that the catalyst (Fe3+) concentration values more than 0.2 mM have a negative effect on the mineralization rate of BB3. The mineralization of BB3 aqueous solution was
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followed by total organic carbon (TOC) measurements. The mineralization ratio was found upper to 98%. Decolorization of a solution can be observed when the chromophore responsible of the color is chemically destroyed but this does not constitute an indication of elimination of the organic compounds from the treated solution. In addition, the oxidation treatment can lead to a more toxic solution when the formed chemical intermediates are more toxic than the parent dye molecule. Thus, information relative to chemical compounds produced during the decolorization process constitues an important issue. In order to determine aromatic degradation products of BB3, several experiments were performed by using chromatographic and mass analysis. Generation of short chain carboxylic acids is expected from the oxidative breaking of the aryl
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moiety of aromatic products. The qualification and quantification of short chain carboxylic acids was performed by ion-exclusion chromatography. The obtained results indicate the formation of several carboxylic acids. We could only determine oxalic and oxamic acids which are the dominant ones. The ion chromatography analysis allowed qualitative and quantitative monitoring of inorganic ions resulting from the mineralization of BB3. The formed inorganic ions were determined as ammonium, nitrate, diethylammonium and methylammonium by retention time comparison and standard addition method. Based on the identified intermediates, a general mineralization mechanism was proposed.
Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2009). Electro-Fenton removal of the cationic dye Basic Blue 3 by using carbon felt cathode. Journal of Environmental Engineering and Management, 19(5), 267-275.

Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan Removal of Basic Blue 3 from Water by Electrochemically Generated Fentons Reagent The 6th Spring Meeting of the International Society of Electrochemistry, Foz do Iguau, Brasil, 16-19 March 2008. (Poster presentation).
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Paper 2
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Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, 2009. Electro-Fenton removal of the cationic dye Basic Blue 3 by using carbon felt cathode.
Journal of Environmental Engineering and Management, 19(5), 267-275.
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3.1.2. Pesticides
Pesticides are natural or synthetic substances used to kill various kinds of animal and plant pests. Pesticides cover a wide range of products including weedkillers, insecticides, fungicides, wood preservatives and rodenticides. Of the pesticides that are used far less than 1% actually reaches a target organism; the rest ends up contaminating the air, soil, water, plants and animals. As a result, pesticides constitues a potential threat to human health because of their solubility in lipid and accumulation in our fatty tissues in a process called bioconcentration. Biomagnification is what happens when organisms eating contaminated organisms concentrate the pesticides and then in turn are eaten by other organisms. As a result those on the top of the food
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chain (all meat-eating humans) are most at risk because the concentration is magnified at each step of the food chain. Furthermore because pesticides are designed to kill organisms due to their neurological or reproductive toxicity they also have many similar deleterious effects in humans, and many show adverse effects on the immune system at very low doses. Pesticides have many ecological effects of concern as well. Ecological effects are often considered to be an early warning indicator of potential human health impacts. In the environment pesticides can kill organisms, cause cancers, tumors and lesions in fish and wildlife, suppress the immune system, cause reproductive failure, damages on DNA, disrupt the endocrine (hormonal) system, and cause physiological birth defects (teratogenic effects) (Sazova, 2004). These substances have been used extensively to increase the agricultural productivity as well as their household usage. Food and Agriculture Organization reported that more than 1.2 million metric tons of pesticides were sold to the agricultural sectors during the middle of the last decade (Shulze et al., 2002). These substances are in fact very effective against the harmful microorganisms, weed and insects in order to increase agricultural yields; however, because of their hazardous nature, the waste and rinsate from spray and storage equipment have been considered as one of the major threats to the environment. Thus, treatment of effluents containing pesticides is of environmental importance. In this study we investigated the ability of the electro-Fenton process to eliminate three herbicides belonging to different chemical family: Picloram (systemic herbicide), propham (carbamate herbicide),
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chlopyralid (systemic herbicide) and a organophosphorus non systemic insecticide: Azinphos-methyl.
3.1.2.1. Picloram
Picloram (4-amino-3,5,6-trichloro-2-pyridincarboxylic acid) is a herbicide used for broadleaf weed control in pasture and rangeland, wheat, barley, oats, and for woody plant species (Fig. 3.3) (Ahrens, 1994). Picloram is moderately to highly persistent in the soil environment, with reported field half-lives from 20 to 300 days and an estimated average of 90 days (Wauchope et al., 1992). Photodegradation is significant only on the soil surface and volatilization is practically nil. Degradation by
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microorganisms is mainly aerobic. Increasing of soil organic matter enhances the sorption of picloram and the soil residence time (Ahrens, 1994). Picloram is poorly bounded to soils, although its adsorption became better by soils with higher proportions of organic matter (Ahrens, 1994). It is soluble in water, and therefore may be mobile (Kidd and James, 1991). These properties, combined with its persistence, mean it may constitute a risk of groundwater contamination.
NH2 Cl
Cl
O Cl N OH
Figure 3.3. Chemical structure of picloram
The degradation and removal of picloram from water was investigated by several authors in the literature. Ghauch (2001) used zero-valent iron for the degradation of picloram. He observed that picloram is converted to 4-amino-2pridylcarbinol molecule in one hour reaction but it is not degraded completely to nonhazardous species. Rahman and Munuer (2005) used heteregenous photocatalysis in the presence of different kinds of titanium oxide catalysts. Adsorption process by using the calcinated hydrotalcite (Pavlocia, 2005) and calcinated Mg-Al-CO3-LDH (Cardoso and Valim, 2006) as sorbents for the removal of picloram from water was
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also performed. According to literature there was no study on the degradation and mineralization of picloram by using electro-Fenton process. In this part of the study, we investigated the removal of picloram from its aqueous solution by electro-Fenton technique using carbon felt cathode. Firstly, the degradation kinetics of picloram was investigated. Kinetic results evidence a pseudofirst-order reaction, with an oxidation reaction rate constant of picloram by hydroxyl radicals of (2.73 0.08) x 109 M-1 s-1. The effect of applied current and catalyst concentration on the degradation and mineralization of picloram was also investigated. The optimum applied current and catalyst concentration values for the degradation of picloram was determined as 300 mA and 0.2 mM Fe3+, respectively. Mineralization of picloram aqueous solutions was followed by the total organic
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carbon (TOC) analysis. At the end of 8 h of electrolysis, 95% of the initial TOC was removed. The HPLC analysis of electro-Fenton treated aqueous solution of picloram (I) showed the formation of several intermediate products. In order to determine these products several analysis were performed by using some chromatographic techniques. LC-MS analysis showed that picloram degradation has led to the formation of several products but a dominant aromatic intermediate; 4-amino dichloro hydroxy picolinic acid. 2,3,5-Trichloro-pyridin-4-ylamine, 3,5,6-Trichloro-pyridine-2-carboxylic acid, 4 amino-5,6-dichloro-3-hydroxy-pyridine-2-carboxylic acid and 5,6-Dichloro-3-
hydroxy-pyridine-2-carboxylic acid were identified by GC-MS analysis. The oxalic, oxamic, glyoxylic, glycolic, and formic acids were detected by ion-exclusion chromatography as short-chain carboxylic acids. The formation of chloride, nitrate and ammonium was observed during the electro-Fenton treatment of picloram. The identified by-products allowed to propose a mineralization pathway for the picloram mineralization.
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Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2008) Degradation of picloram by the electro-Fenton process. Journal of Hazardous Materials, 153(1-2), 718-727.
The following presentations in a congress are related to this work: 1. Ali zcan, Mehmet A. Oturan, Ycel ahin, A. Sava Koparal Degradation of picloram by the electro-Fenton process Journees dElectrochimie 2007, Lyon, France, 2-6 July 2007 (Poster presentation).
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2. Ali zcan, Ycel ahin, Mehmet A. Oturan Identification Of Oxidation By-Products Of Picloram 6th Aegean Analytical Chemistry Days, Denizli, Turkey, 9-12 October 2008 (Poster presentation).
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Paper 3
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Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2008) Degradation of picloram by the electro-Fenton process, Journal of Hazardous Materials, 153(1-2), 718-727
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3.1.2.2. Propham
Propham is a carbamate herbicide used for the control of weeds in alfalfa, clover, flax, lettuces, afflow, spinach, sugar beets and pees. It prevents cell division and acts on meristematic tissues. Moreover, it could be degraded into aniline metabolites which are more dangerous substances than the parent molecule (Orejuela and Silva, 2004). The presence of this herbicide in surface water was reported by Meister (2000). On the other hand, the maximum allowed amount of this substance in water intented to human consumption is 0.1 g L-1 in water intended for human consumption according to the EU Directive 98/83 (EC, 1999). Therefore, the removal of this substance from aqueous solutions has great importance.
O
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N H
Figure 3.3. Chemical structure of propham
In this part of the study, the removal of a carbamate herbicide, propham, from aqueous solution has been carried out by the electro-Fenton technique. The degradation kinetics of propham evidenced a pseudo-first-order degradation. The absolute (or second-order) reaction rate constant of the reaction between propham and hydroxyl radicals was determined as (2.20.10) x 109 M-1 s-1. The mineralization of propham was followed by the total organic carbon (TOC) removal. The optimal Fe3+ concentration was found as 0.5 mM at 300 mA. 94% of initial TOC of 0.25 mM propham aqueous solution was removed in 8 h. HPLC, GC-MS and LC-MS analysis were used to determine the aromatic byproducts of propham oxidation and the results are given in Table 1. The HPLC chromatograms showed that the degradation of propham has led to formation of several intermediates. Two of them exhibits dominant peaks but they have not been identified by HPLC. A single electrolysis was performed for 15 min and the formed aromatic intermediates were extracted with dichloromethane, and then the obtained extract was analyzed by GC-MS. Two dominant peaks in the GC chromatogram were identified as o- and p-hydroxypropham based on their molecular ion and mass fragmentation. Moreover, we prepared the trimethylsilyl (TMS) derivatives of the
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intermediates and identified a new product which was different from those obtained by using HPLC and GC-MS analysis. In the LC-MS analysis, two dominant peaks in the LC chromatogram were identified as p- and o-hydroxypropham according to (M+1)+ values and mass fragmantations. The oxidative breaking of the aryl moiety of aromatic products forms the short chain carboxylic acids during the electro-Fenton process. These substances were identified and quantified by ion-exclusion chromatography with two well-defined peaks related to oxalic (tr: 7.04 min) and oxamic (tr: 10.60 min) acids as ultimate carboxylic acids. Oxamic acid can be produced from the degradation of nitrogen containing by-products of propham. In the first 80 min of the electrolysis, the formation of maleic, glyoxylic, lactic, formic, acetic and fumaric acids were also
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observed. The nitrogen atom found in the propham structure was converted to nitrate and ammonium ions which were identified by ion chromatography analysis. The formation rate of ammonium ions in the first 30 min of the electrolysis was very fast. After that time, ammonium formation rate gradually decreased and reached a steady state value. This behaviour can be explained via the slow degradation rate of oxamic acid because it forms stable iron complexes and shows resistance to the mineralization. The identified by-products allowed proposing a pathway for the propham mineralization.
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Ali zcan, Ycel ahin, Mehmet A. Oturan (2008) Removal of propham from water by using electro-Fenton technology: Kinetics and mechanism Chemosphere, 73(5), 737-744.

1. Ali zcan, Ycel ahin, Mehmet A. Oturan Mineralization of Propham in Aqueous Medium by using an
Electrochemical Advanced Oxidation Process The 58th Annual Meeting of the 9-14 International September Society 2007 of
Electrochemistry,
Banff,
Canada,
(Oral
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presentation).
2. Ali zcan, Ycel ahin, Mehmet A. Oturan Determination Of Degradation Intermediates Of Propham With
Chromatographic And Mass Spectrometric Analysis 6th Aegean Analytical Chemistry Days, Denizli, Turkey, 9-12 October 2008. (Poster presentation)
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Ali zcan, Ycel ahin, Mehmet A. Oturan (2008) Removal of Propham from Water by Using Electro-Fenton Technology; Kinetics and Mechanism Chemosphere,, 73(5), 737-744
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3.1.2.3. Clopyralid
Clopyralid (CLPYD, 3,6-dichloro-2-pyridinecarboxylic acid) is a systemic herbicide registered by US environmental protection agency (US EPA, 1998) for control of weeds and woody plants on rangeland and permanent grass pastures, noncropland areas and rights-of-way. It affects plant cell respiration and growth. This herbicide is generally active in the soil and may be persistent in soils under anaerobic conditions and with low microorganism content. The half-life in soil can range from 15 to more than 280 days. Degradation products have not been identified in the soil up to now (Corredor et al., 2006). Due to its high solubility in water, this herbicide is not adsorbed onto soil particles. It may leach into ground-water by surface water in
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filtration and constitute a potential threat to the human health and environment. Therefore, the removal of this herbicide from water resources is very important.
Cl
O Cl N OH
Figure 3.4. Chemical structure of clopyralid
The removal of CLPYD from aqueous solutions was performed by the electroFenton process using carbon felt cathode. The decay kinetics well fitted to pseudofirst order reaction and absolute rate constant of the oxidation reaction of CLPYD was determined as (4.4 0.2) x 108 M-1 s-1. Mineralization ability of the system was followed by the chemical oxygen demand (COD) analysis. The total mineralization was achieved at almost 120 and 240 min electrolysis for 1.5 and 3.0 mM CLPYD solutions, respectively. The obtained results indicate that the electro-Fenton process is very effective for the removal of this pollutant from water. HPLC analysis of electro-Fenton treated solutions of CLPYD showed the formation of several by-products but three of them were dominant. The CLPYD peak was rapidly decreased and the peaks corresponding to the by-products were appeared and increased in the first 5 min. After that time, they gradually decreased and completely disappeared in 20 min. This situation indicates that the formed by-
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products were unstable at the given oxidizing conditions. Therefore, they did not accumulate during the electrolysis. Moreover, the gas chromatography-mass spectrometry (GC-MS) analysis of the samples gave no meaningful results. Formic, oxalic, maleic, fumaric, oxamic and glyoxylic acids were determined as short-chain carboxylic acids. While the formation rates of oxalic, maleic and oxamic acids are very high in the first 90 min, after that time, their accumulation rates gradually decreased. The ion chromatography analysis indicated the formation of ammonium, nitrate and chloride ions. The formation rate of chloride ions was very high in the first 30 min of electrolysis. The released quantity of chloride ions was almost reached to its maximal value at 60 min. After that time, its concentration is nearly the same. The
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stoichiometric ratio of initial chlorine was achieved at the end of the electrolysis. Nitrogen atom found in the CLPYD structure was rapidly converted to ammonium ions in the first 30 min of the electrolysis. After that time, ammonium formation rate gradually decreased and reached a steady state value. This behaviour can be explained via the slow degradation rate of oxamic acid because it forms stable iron complexes and shows resistance to the mineralization. The formation of nitrate ions can be attributed to the oxidation of ammonium ions on the Pt anode. The obtained concentrations of NO3- and NH4+ ions showed that 98% of the initial nitrogen was converted to the NH4+ ions during the electro-Fenton process. We quantified almost 99% of initial nitrogen as NH4+ and NO3- ions after 6 h electrolysis. Based on these intermediates, a general oxidation mechanism was proposed in acid medium.
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Ali zcan, Nihal Oturan, Ycel ahin, Mehmet A. Oturan (2010) Electro-Fenton treatment of aqueous Clopyralid solutions International Journal of Environmental Analytical Chemistry (in press).

Ali zcan, Nihal Oturan, Ycel ahin, Mehmet A. Oturan Electro-Fenton treatment of aqueous Clopyralid solutions ,5th European Conference on Pesticides and Related Organic Micropollutants
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in the Environment and 11th Symposium on Chemistry and Fate of Modern Pesticides, October 22-25, 2008, Marseille, France. (Poster presentation)
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Paper 5
Ali zcan, Nihal Oturan, Ycel ahin, Mehmet A. Oturan (2010) Electro-Fenton Treatment of Aqueous Clopyralid Solutions International Journal of Environmental Analytical Chemistry, in press.
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3.1.2.4. Azinphos-Methyl
Azinphos-methyl (AZPM) is an organophosphorus non-systemic pesticide widely used to control a variety of insects in food and non-food crops, ornamentals and forest trees (Fig. 3.5). It is mainly applied as a foliar spray during the growing season. It has been reported that AZPM had the seventh highest use of all pesticides in the United States in 1997 (US EPA, 1998). Although its high toxicity and widespread usage, a limited number of studies was reported in literature for the removal of AZPM from water resources. To the best of our knowledge, the degradation of AZPM by the electro-Fenton process was not reported previously in the literature. This part of the study deals with the degradation of AZPM and its commercial
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formulation, (GMWP25), by the electro-Fenton process using carbon felt cathode. The degradation kinetics and mineralization efficiency was deeply investigated. The identification and evolution of the degradation intermediates was also performed by HPLC, GC-MS and IC analysis. Based on identified intermediates, a general reaction sequence was proposed for the degradation of AZPM in acidic media by electrochemically generated hydroxyl radicals.
O S N N N S P OCH3 OCH3
Figure 3.5. Chemical structure of azinphos-methyl
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The study related to the work on AZPM resulted to the following publication in 5th European Conference on Pesticides and Related Organic Micropollutants in the Environment which is published in the congress proceedings.
Ali zcan, Ycel ahin, Mehmet A. Oturan (2008) Mineralization of a commercial formulation of Azinphos-methyl, Gusathion M WP 25, in aqueous medium by indirect electrochemical advanced oxidation method, Proceedings of 5th European Conference on Pesticides and Related Organic Micropollutants in the Environment and 11th Symposium on Chemistry and Fate of Modern Pesticides, October 22-25, 2008, Marseille, France.
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Paper 6
Ali zcan, Ycel ahin, Mehmet A. Oturan (2008) Mineralization of a commercial formulation of Azinphos-methyl, Gusathion M
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WP 25, in aqueous medium by indirect electrochemical advanced oxidation method. Proceedings of 5th European Conference on Pesticides and Related Organic Micropollutants in the Environment and 11th Symposium on Chemistry and Fate of Modern Pesticides, October 22-25, 2008, Marseille, France.
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3.2. Investigation of the H2O2 production ability of carbon sponge (CS) as a novel cathode material for electro-Fenton process
Considerable efforts have been made by many researchers to find appropriate treatment systems in order to remove pollutants and impurities from wastewaters emanated from the textile industries. Among the treatment Technologies developed, the advanced oxidation processes (AOPs) are considered as the most attractive methods for the treatment of water and wastewater containing toxic, persistent and non-biodegradable pollutants. AOPs are based on the generation of very reactive nonselective transient oxidizing species such as hydroxyl radicals (OH), which were identified as the dominant oxidizing species. In this context, the electro-Fenton
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process constitute an emergent and promising wastewater treatmrnt method. Oxidation power of the electro-Fenton system was mainly related to H2O2 production ability of cathode material used in the electrolysis. Therefore, the cathode materials which have high H2O2 production ability are very important for the effective destruction of pollutants since the formation rate of hydroxyl radicals through Fentons reaction is conditioned by H2O2 formation rate on the cathode employed. In this manner, several electrode materials such as mercury pool (Oturan and Pinson, 1995), graphite (Do and Chen, 1994), reticulated vitreous carbon (Alvarez-Gallegos and Pletcher, 1999), carbon felt (Oturan, 2000; Oturan et al., 2000 and 2001), O2-fed carbon polytetrafluoroethylene (Brillas et al., 1996; Boye et al., 2003; Sirs et al., 2007), and activated carbon fiber (Wang et al., 2005) were investigated as the cathode material in the electro-Fenton process. Consequently, we have investigated carbon sponge (CS) as a novel cathode material for the first time in the literature. The efficiency of the CS electrode was comparatively discussed with carbon felt (CF) electrode for degradation of the synthetic dye, Basic Blue 3 (BB3). Fig. 3.6 shows the H2O2 concentration produced on the CS and CF electrodes as a function of time. As can be seen, the electrogeneration of H2O2 on both electrodes showed similar behaviours. In the first fifty minutes of electrolysis, there was a fast electrogeneration of H2O2 but after that time the H2O2 accumulation rate was decreased and reached to a steady state value when its generation rate at the cathode (Eq. 2) and its decomposition rate at the anode become equal. The concentration of H2O2 reached via CS and CF electrodes was 8.05 and 2.70 mM, respectively, at the
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end of the 180 min. electrolysis. The results obtained with the CS was nearly three times higher than that of CF. According to these results, it can be concluded that CS was a favorable cathode material for the electrogeneration of H2O2. The effect of some operational parameters such as applied current value, type of supporting electrolyte, O2 flow rate, pH and temperature on the generation of H2O2 by CS was investigated. The optimal current value for the H2O2 production was 100 mA (5.6 mA cm-2). The temperature and O2 flow rate have also a significant effect on the amount of electrogenerated H2O2, whereas supporting electrolyte and pH of the solution have a slight affect. The degradation and mineralization of the BB3 were followed by using HPLC and TOC analysis, respectively. The degradation and mineralization of BB3 using CS cathode was found faster than that of CF cathode. At
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the end of eight hour electrolysis under the same conditions, 91.6% and 50.8% of the initial TOC of the BB3 aqueous solution was removed by using CS and CF cathodes, respectively. The mineralization current efficiency (MCE) of CS electrode was four times higher than that of CF electrode. The results showed that the CS electrode provides an alternative cathode material for future designing of water treatment system in the electro-Fenton process.
9
[H2O2] / mM
0 0 50 100 Time / min

Figure 3.6. The amount of electrogenerated H2O2 on the CS () and CF () surface as a function of time at room temperature. [Na2SO4] : 0.05 M, I : 100 mA, pH : 3, V : 0.125 L, O2 flow rate : 100 mL min-1.
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200
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Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2008) Carbon sponge as a new cathode material for the electro-Fenton process. Comparison with carbon felt cathode and application to degradation of synthetic dye basic blue 3 in aqueous medium. Journal of Electroanalytical Chemistry, 616 (1-2), 71-78.
The following presentation in a congress is also related to this work:
Ali zcan, Ycel ahin, Nihal Oturan, Mehmet A. Oturan H2O2 production ability of carbon sponge(CS) as a novel cathode material for
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the electro-Fenton process. Electrochimie et ses Applications Industrielles et Environnementales RNE 05 (Cinquime Rencontre Nationale d'Electrochimie), Agadir (Marocco), 27-29 March, 2008. (Poster presentation).
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Paper 7
Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2008) Carbon sponge as a new cathode material for the electro-Fenton process. Comparison with carbon felt cathode and application to degradation of synthetic dye basic blue 3 in aqueous medium Journal of Electroanalytical Chemistry, 616 (1-2), 71-78.
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3.3. Investigation of the efficiency of boron doped diamond (BDD) anode in the electro-Fenton process
The efficiency of the electro-Fenton technique mainly depends on the cathode material used in the electrolysis. On the other hand, the anode material has also a prominent effect on the process efficiency, in particular in anodic oxidation and in electro-Fenton process when a high O2 evolution overvoltage electrode (mixed metal oxides, MO2 or boron doped diamonds, BDD is used as anode) is employed instead of the Pt electrode as common anode material. The use of different anode materials has increased lately. In this context, among the variety of electrode materials the boron doped diamond (BDD) has been attracted great attention because of its high stability, efficient OH generation rate thanks to its significantly high O2 evolution overpotential and mineralization efficieny. This electrode allows in-situ production of hydroxyl radicals at large quantities by the oxidation of water (Eq. 3.1) or hydroxide ion (Eq. 3.2) on the electrode surface. H2O OHads + H+ + e OH OHads + e pH10 (3.1) (3.2)
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In this last part of our study we investigated the oxidative degradation of propham aqueous solutions at the anodic oxidation conditions in order to test the ability of the BDD electrodes in the production of hydroxyl radicals, the oxidation of propham aqueous solutions at the anodic oxidation conditions were performed. The effect of important operating parameters such as applied current, temperature, pH, and types of the supporting electrolyte on the degradation rate and mineralization efficiency were investigated. The concentration of OH radical depends on the applied current value. Therefore, here, the effect of applied current values on the degradation rate of propham was examined by using the applied current values of 30, 50, 100, 150, 300, and 500 mA. When the applied current value increased from 30 mA to 50 mA, a slight increase was observed in the degradation rate of propham. Beyond this value, the effect of applied current is not significant. In all cases, the degradation of propham was completed within 180 min. In order to clarify the oxidation ability of the system, we performed the TOC analyses of the samples after 180 min electrolysis. The TOC removal values were increased by increasing applied current. It was
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interesting to note that while the initial degradation rate of propham was almost the same for all applied current values, the TOC removal values greatly increased at higher applied current values. This situation can be explained in the following way. The aromatic reaction intermediates formed by the oxidation of propham are more reactive towards hydroxyl radicals than propham. By increasing applied current values, the formation rate of OH also increased and these radicals were consumed simultaneously by the aromatic and aliphatic by-products. As a result the degradation rate of propham did not change significantly. On the other hand, the TOC removal values remained almost constant at 300 and 500 mA. The results show that the optimal current value was about 300 mA for mineralization of propham. The effect of temperature on the anodic oxidation behavior of propham was
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investigated at different temperature values between 15 and 35 C at 100 mA constant current. The degradation of propham showed similiar trend for all temperature values. By increasing the temperature from 15 C to 35 C, a significant increase was obtained in the degradation rate of propham. The pH of electrolyses medium is the other important parameter for the electrochemical oxidation procedures. The results indicated that the efficiency of the process was increased in acidic media. In order to verify the influence of the supporting electrolyte on the degradation kinetics and mineralization efficiency of propham aqueous solutions, the experiments were performed in acidic medium (pH 3) containing different supporting electrolytes as 0.05 M Na2SO4, 0.1 M NaNO3, LiClO4 and NaCl. The degradation rate of propham was slightly increased when the Na2SO4 was used as supporting electrolyte instead of NaNO3. The complete degradation of propham almost took place in a 180 min electrolyses period in the presence of Na2SO4, NaNO3 and LiClO4. However, it finished in 15 min in the case of NaCl. The TOC removal values of propham mineralization were increased in the following order: NaCl < NaNO3 < LiClO4 < Na2SO4. Although the use of NaCI as supporting electrolyte has a very important effect on the propham degradation kinetics, this effect was not seen on the mineralization efficiency. The oxidation by-products such as aromatics, short-chain carboxylic acids, and inorganic ions were determined by the HPLC, LC-MS, GC-MS, and IC methods.
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Finally, an oxidative degradation pathway of propham by OH radicals generated on BDD anode in aqueous medium was proposed. In this part of the study, the combination of BDD electrode with carbon sponge (CS) cathode in the electro-Fenton technique was also investigated using propham as a model pollutant. The obtained results pointed out that the combination of BDD and CS electrodes as anode and cathode in the electro-Fenton process was the most efficient. Another result of this study was the effects of BDD electrode on the accumulation of the oxidation by-products of propham during the electro-Fenton process. The intermediates especially oxamic acid and ammonium displayed different accumulation charecteristics in the case of the use of BDD or Pt anodes in the electroFenton processes.
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The thorough results of this section are included in the following paper (Paper 8 and 9).
Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2008) Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: Influence of experimental parameters on degradation kinetics and mineralization efficiency Water Research, 42(12), 2889-2898. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2009) A comparative study on the efficiency of electro-Fenton process in the removal of propham from water Applied Catalysis B: Environmental, 89(3-4), 620-626.
The following presentations in congress are related to this work:
Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan Anodic Oxidation of Propham in Water using BDD Electrode The 6th Spring Meeting of the International Society of Electrochemistry, Foz do Iguau, Brasil, 16-19 March 2008. (Poster presentation).
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Nihal Oturan, Ali zcan, Ycel ahin, Mehmet A. Oturan Investigation of oxidation power of the electro-Fenton process using carbon sponge (CS) cathode and boron doped diamond (BDD) anode Electrochimie et ses Applications Industrielles et Environnementales RNE 05 (Cinquime Rencontre Nationale d'Electrochimie), Agadir (Marocco), 27-29 March, 2008. (Poster presentation).
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Paper 8
Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan(2008) Propham mineralization in aqueous medium by anodic oxidation using borondoped diamond anode: Influence of experimental parameters on degradation kinetics and mineralization efficiency Water Research, 42(12), 2889-2898.
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Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan (2009) A comparative study on the efficiency of electro-Fenton process in the removal of propham from water Applied Catalysis B: Environmental, 89(3-4), 620-626.
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US
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(1998),
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organophosphate pesticides, azinphos methyl, Washington DC: Office of Prevention, Pesticides and Toxic Substances. Wang, A., Qu, J., Ru, J., Liu, H., Ge, J. (2005), Mineralization of an azo dye Acid Red 14 by electro-Fenton's reagent using an activated carbon fiber cathode, Dyes and Pigments, 65, 227-233. Wauchope, R. D., Buttler, T. M., Hornsby, A. G., Augustijn Beckers, P. W. M., Burt, J. P. (1992) SCS/ARS/CES Pesticide properties database for environmental decisionmaking, Rev. Environ. Contam. Toxicol., 123, 10-12.
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Curriculum Vitae Name Surname Age Sex : Ali : zcan : 30 :M
Marial Status : Married EDUCATION 1998-1999 : Prep School, School of Foreign Languages, Anadolu University, Turkey 1999-2003 : Department of Chemistry, Faculty of Sciences, Anadolu University, Turkey
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2003-up to date
: Department of Chemistry, Graduate School of Sciences, Anadolu University, Turkey(PhD)
2006-up to date
: PhD thesis student in Co-tutelle de thse at Paris-Est Marne-laValle university
EMPLOYMENT RECORD 2003- up to date : Department of Chemistry Faculty of Sciences, Anadolu University, Research and Teaching Assistant LANGUAGE Turkish (Mother language) English SCHOOL ACHIEVMENTS Awarded by the first price of Department of Chemistry. Awarded by the first price of Faculty of Sciences. AWARDED FELLOWSHIPS 2001-2003 : Undergraduate Fellowships, Scientific Human Resources Development (BAYG), The Scientific and Technical Research Council of Turkey (TUBITAK) 2003-2008 : Graduate Fellowships, Scientific Human Resources Development (BAYG), The Scientific and Technical Research Council of Turkey (TUBITAK)
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SCIENTIFIC INTERESTS Electroanalyticalchemistry, electro-Fenton technology, environmental analytical chemistry, removal of hazardous materials, solid phase extraction, quartz crystal microbalance(QCM), electrochemical DNA biosensors, modified electrodes.
LIST OF RECENT SELECTED PUBLICATIONS
1. Arzu Ersz, Adil Denizli, Ali zcan, Rdvan Say, Molecularly imprinted ligand exchange recognition assay of glucose by quartz crystal microbalance, Biosensors and Bioelectronics, (2005), 20, 21972202.
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2. Ali zcan, Ycel ahin, Mehmet zsz, Servet Turan , "Electrochemical Oxidation of ds-DNA on Polypyrrole Nanofiber Modified Pencil Graphite Electrode", Electroanalysis, (2007), 19(21), 2208-2216. 3. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Degradation of picloram by the electro-Fenton process, Journal of Hazardous Materials (2008), 153(1-2), 718-727. 4. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Carbon sponge as a new cathode material for the electro-Fenton process. Comparison with carbon felt cathode and application to degradation of synthetic dye basic blue 3 in aqueous medium, Journal of Electroanalytical Chemistry (2008), 616 (1-2), 7178. 5. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: Influence of experimental parameters on degradation kinetics and mineralization efficiency, Water Research (2008), 42(12), 2889-2898. 6. Ali zcan, Ycel ahin, Mehmet A. Oturan, Removal of Propham from Water by Using Electro-Fenton Technology; Kinetics and Mechanism, Chemosphere (2008), 73(5), 737-744. 7. Ali zcan, Mehmet A. Oturan, Nihal Oturan, Ycel ahin, "Removal of Acid Orange 7 from water by electrochemically generated Fentons reagent", Journal of Hazardous Materials (2009), 163(2-3), 1213-1220.
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8. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, A comparative study on the efficiency of electro-Fenton process in the removal of propham from water, Applied Catalysis B: Environmental (2009), 89(3-4), 620-626. 9. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Electro-Fenton removal of the cationic dye Basic Blue 3 by using carbon felt cathode J. Environ. Eng. Manage., (2009), 19(5), 267-275. 10. Ali zcan, Ycel ahin, "Selective and Sensitive Voltammetric Determination of Dopamine in Blood by Electrochemically Treated Pencil Graphite Electrodes", Electroanalysis, (2009), 21(21), 2363-2370. 11. Ali zcan, Nihal Oturan, Ycel ahin, Mehmet A. Oturan, Electro-Fenton Treatment of Aqueous Clopyralid Solutions, International Journal of
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Environmental Analytical Chemistry, (2010), in press. 12. Mutlu Sahin, Levent zcan, Ali zcan, Betl Usta, Ycel Sahin, Kadir Pekmez, The substituent effects on the structure and surface morphology of polyaniline, J. Appl. Polym. Sci., (2010), 115(5), 3024-3030.
PROCCEDING 13. Ali zcan, Ycel ahin, Mehmet A. Oturan, Mineralization of a commercial formulation of Azinphos-methyl, Gusathion M WP 25, in aqueous medium by indirect electrochemical advanced oxidation method, In Proceedings of 5th European Conference on Pesticides and Related Organic Micropollutants in the Environment and 11th Symposium on Chemistry and Fate of Modern Pesticides, October 22-25, 2008, Marseille, France.
PRESENTATION IN INTERNATIONAL/NATIONAL CONFERENCES 1. Ali zcan, Muharrem Karabrk, Rdvan Say, Arzu Ersz, Removal of heavy metals by using polymer/organoclay nanocomposites, IV. National Congress of Chromatography, 17-19 September 2003, Ankara, Turkey. 2. Ali zcan, Levent zcan, Ycel ahin, Pnar Kara-Kadayfclar, Dilsat zkanArksoysal, Mehmet zsz, Direct electrochemical determination of ds-DNA using GC-polypyrrole electrode, VI. Electrochemistry Days, 29 June-01 July 2005, Eskisehir, Turkey
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3. Deniz Hr, Ali zcan, Ycel ahin, Electrochemical behaviour of 3-phenyl-1-(2thienyl)-2-propyn-1-one and effect of benzotriazole, VI. Electrochemistry Days, 29 June-01 July 2005, Eskisehir, Turkey 4. Levent zcan, Ali zcan, Ycel ahin, Muhittin Arslanyolu, Pnar KaraKadayfclar, Dilat zkan-Arksoysal, Mehmet zsz, Direct Electrochemical Determination of DNA Hybridization Using GC-Polypyrrole Electrode, VI. Electrochemistry Days, 29 June-01 July 2005, Eskisehir, Turkey 5. Levent zcan, Ali zcan, Ycel ahin, Pnar Kara-Kadayfclar, Dilat zkanArksoysal, Mehmet zsz, Electrochemical detection of tumor necrosis factor gene sequence based on imprinted polypyrrole modified electrode, XII. International Biomedical Science and Technology Symposium, 20-23 September
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2005, Izmir, Turkey. 6. Ali zcan, Ycel ahin, Nihal Oturan, Mehmet A. Oturan, Removal of Acid Orange 7 from water by electrochemically generated Fentons reagent, Journees dElectrochimie 2007, Lyon, France, 2-6 July 2007 7. Ali zcan, Mehmet A. Oturan, Ycel ahin, A. Sava Koparal, Degradation of picloram by the electro-Fenton process, Journees dElectrochimie 2007, Lyon, France, 2-6 July 2007 8. Ali zcan, Ycel ahin, Mehmet A. Oturan, Mineralization of Propham in Aqueous Medium by using an Electrochemical Advanced Oxidation Process, The 58th Annual Meeting of the International Society of Electrochemistry, Banff, Canada, 9-14 September 2007 9. Ycel ahin, Levent zcan, Ali zcan, Betl Ercan and Mzeyyen Claz, Substituent Effect on theMorphology of Polyanilines, German-Turkish University Conference and Project Marketplace on Applied Research and Innovation, 26-28 February 2007, Germany. 10. Ycel ahin, Mutlu ahin, Levent zcan, Ali zcan and Betl Ercan, Synthesis, Characterization and Electrochemical Behaviour of Soluble Fluoro- and ChloroPolyaniline, 58th Annual Meeting of the International Society of
Electrochemistry" S08-P-050, Banff, Canada, 9-14 September, 2007 11. Levent zcan, Mzeyyen Claz, Ali zcan, Mutlu ahin, Ycel ahin, Servet Turan and Hilmi Yurdakul, The effect of dopants on the morphology of
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polyaniline, 18. National Electron Microscopy Congress With International Participation, 26-29 August 2007, Eskisehir, Turkey 12. Ali zcan, Sabriye Perin, Levent zcan, Ycel ahin, Gleren Alsancak, Servet Turan and Hilmi Yurdakul, Preparation and morphological investigation of nanostructured polypyrrole films, 18. National Electron Microscopy Congress With International Participation, 26-29 August 2007, Eskisehir, Turkey 13. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Anodic Oxidation of Propham in Water using BDD Electrode, The 6th Spring Meeting of the International Society of Electrochemistry, Foz do Iguau, Brasil, 16-19 March 2008. 14. Ali zcan, Ycel ahin, A. Sava Koparal, Mehmet A. Oturan, Removal of
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Basic Blue 3 from Water by Electrochemically Generated Fentons Reagent, The 6th Spring Meeting of the International Society of Electrochemistry, Foz do Iguau, Brasil, 16-19 March 2008. 15. Ali zcan, Ycel ahin, Nihal Oturan, Mehmet A. Oturan, H2O2 production ability of carbon sponge(CS) as a novel cathode material for the electro-Fenton process, Electrochimie et ses Applications Industrielles et Environnementales RNE 05 (Cinquime Rencontre Nationale d'Electrochimie), Agadir (Marocco), 27-29 March, 2008. 16. Nihal Oturan, Ali zcan, Ycel ahin, Mehmet A. Oturan, Investigation of oxidation power of the electro-Fenton process using carbon sponge (CS) cathode and boron doped diamond (BDD) anode, Electrochimie et ses Applications Industrielles et Environnementales RNE 05 (Cinquime Rencontre Nationale d'Electrochimie), Agadir (Marocco), 27-29 March, 2008. 17. Ali zcan, Ycel ahin, Mehmet zsz, Preperation of an electrochemical DNA biosensor based on the polypyrrole modified pencil graphite electrode, XIV. International Biomedical Science and Technology Symposium, Mula, Turkey, 37 May, 2008. 18. Ali zcan, Nihal Oturan, Ycel ahin, Mehmet A. Oturan, Electro-Fenton treatment of aqueous Clopyralid solutions, 5th European Conference on Pesticides and Related Organic Micropollutants in the Environment and 11th Symposium on Chemistry and Fate of Modern Pesticides, October 22-25, 2008, Marseille, France.
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19. Ali zcan, Ycel ahin, Mehmet A. Oturan, Determination Of Degradation Intermediates Of Propham With Chromatographic And Mass Spectrometric Analysis, 6th Aegean Analytical Chemistry Days, Denizli, Turkey, 9-12 October 2008. 20. Ali zcan, Ycel ahin, Mehmet A. Oturan, Identification Of Oxidation ByProducts Of Picloram, 6th Aegean Analytical Chemistry Days, Denizli, Turkey, 9-12 October 2008. 21. Ycel ahin, Mutlu ahin, Levent zcan, Ali zcan, Betl Usta, Sabriye Perin and Mzeyyen Ylmaz, Analytical Performance Of Conducting Polymers. 6th Aegean Analytical Chemistry Days, Denizli, Turkey, 9-12 October 2008. 22. Ali zcan, Ycel ahin, Electrochemical determination of dopamine in its
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physicological level in human blood serum without any pretreatment and dilution, 8th International Electrochemistry Meeting, Antalya, Turkey, 8-11 October 2009. 23. Ali zcan, Ycel ahin, Preparation of electrochemically treated pencil graphite electrodes, 8th International Electrochemistry Meeting, Antalya, Turkey, 8-11 October 2009.
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Graduate School of Sciences Electroanalytical Research Laboratory at Chemistry Department

Institut Francilien des Sciences Appliques Laboratoire Gomatriaux et Environnement

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DEGRADATION OF HAZARDOUS ORGANIC COMPOUNDS BY USING ELECTRO-FENTON TECHNOLOGY

DEGRADATION DES POLLUANTS ORGANIQUES PAR LA TECHNOLOGIE ELECTRO-FENTON

Prof. Figen KADIRGAN Prof. Otavio GIL

Examinators: Prof Kadir PEKMEZ

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2.1. Electrochemical system.. 6 2.2. Analytical Measurements...6

3. RESULTS AND DISCUSSION

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3.1. Removal of selected hazardous organic pollutants

Paper 8. 95 Paper 9. 106 REFERENCES CURRICULUM VITEA 114 120

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1.1. Principles of Electrochemical Advanced Oxidation Processes

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(1.5) (1.6) (1.7) (1.8)

1.2. Criteria for selection of organic pollutants

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1.3. Objectives of Study

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2.1. Electrochemical System

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2.2. Analytical Measurements

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3. RESULTS AND DISCUSSION

3.1.1. Synthetic dyes

3.1.1.1. Acid orange 7

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Figure 3.1. The molecular structure of Acid Orange 7

naphthalenedione, salicylic acid, 1,4-benzoquinone, hydroquinone and 1,2,4-

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The following presentations in a congress are related to this work:

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Figure 3.2. Chemical structure of BB3 ((7-Diethylamino-phenoxazin-3-ylidene)-diethylammonium chloride).

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The following presentations in a congress are related to this work:

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chlopyralid (systemic herbicide) and a organophosphorus non systemic insecticide: Azinphos-methyl.

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